Novel telomerization reaction



United States Patent "Ice 3,097,246 NOVEL TELOMERIZATION REACTION Dimitrios V. Favis, Sarnia, Ontario, Canada, assignor to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed Nov. 16, 1960, Ser- No. 69,548

" 8 Claims. (Cl. 260671) This invention rel-ates to telomerization reaction and more particularly to the telomerization reaction between ethylene and an aromatic hydrocarbon.

It was found by N. A. McCall and H. W. Coover (US. Patent 2,824,145) that ethylene could be polymerized with an aromatic hydrocarbon such as benzene or toluene using as catal st EtA1X /TiC1 where X is a halogen, preferably br mine, having a molar ratio less than 1 to form lkylated aromatics. It was found, however, that the yields of alkylated aromatics suitable as lubricating oils were low because of the formation of large quantities of waxy or solid products.

.It has now been found that the preparation of polyalkylated aromatic hydrocarbons suitable as lubricating oils can be prepared in high yield by reacting ethylene with an aromatic hydrocarbon in the presence of a 3-component catalyst containing at least (1) an alkyl compound of a metal of groups I to III of the periodic table; (2) a halide of a transition metal of groups IV-B, V-B, VI-B and VIII of the periodic table, and (3) an alkylhalocyeloalkane,

preferably alkylhalocyclopentane, in an inert diluent. It is critical that the quantity of alkylhalocyclopentane be less than one mole per mole of alkyl radical of the above alkyl compound.

The aromatic hydrocarbon starting material of the inventionhas the general formula:

wherein: Ar is a monoor polyring aromatic nucleus of either fused or benzenoid type such as benzene, diphenyl, naphthalene, anthracene and the like; R is a straight or branched alkyl or cycloalky-l group which is saturated or unsaturated; x=0 to 9, preferably 0 to 1, depending partly on the number of rings in the aromatic nucleus, and is chosen such that at least one free position remains on the aromatic nucleus. The unsubstituted or mono substituted aromatics such as benzene and toluene are preferred due to their cheapness. groups can be the same or difierent, and can be spaced in any relationship to each other; and with polyring aromatics the R groups can be all on the same ring or spaced in any relationship to each other on two or more rings. In addition to aromatics of the above general formula, polyaromatic methanes can be employed such as for example bi-phenylmethane and triphenylmethane.

When x is more than one, the R The products prepared by the process of the invention are mixtures of alkylated aromatics wherein the starting aromatic or alkylaromatic compounds are substituted with one or more alkyl groups up to and including substitution on every available position on the aromatic nucleus. The

alkyl groups attached to the aromatic nucleus by the in- M e=a metal of groups I to III of the periodic table such i as Li, Na, K, Mg, Ca, Sr, Ba, Al, Ga, and In; with Al preferred;

X =a halogen chosen from I, Br, and Cl; and

p=0 to 2 depending on the value of n and the valence of 3,097,246 Patented July 9, 1963 The preferred compound is triethyl aluminum although 'diethyl aluminum chloride has also been found to be highly invention have the following general formula:

MX, where M =a transition metal of groups IV-B, V-B, VI-B, and VIII of the periodic system such as Ti, Zr, V, Cr, Mo, W, and Fe, preferably Ti; X =a halide, preferably Cl; and a=2 to 4 The preferred compound is titanium tetrachloride. The third component of the catalyst is an alkylhalocyc-lopenta-ne having the formula:

.lyst modifier.

The mole ratio of alkyl compound to metal halide in the catalyst should be in the range of 0.1 to 5.0, preferably 0.5 to 0.9. The quantity of alkyl halocyclopentane to the group I to II metal alkyl compound must be less than 0.05 to 0.99 moles. The monomer employed must be ethylene since higher walpha olefins such as propylene were found to give unsatisfactory low viscosity index-high viscosity oils.

The reaction is carried out at atmospheric pressure at a temperature of from about 0 to 130 F., preferably 30 to F. in the presence of an aliphatic, cycloaliphatic, or aromatic hydrocarbon, preferably methylcyclo- 'pentane. The lower the temperature of reaction, the less the formaiton of solid by-products. Examples of suitable diluents that can be employed are the paraflin-s, such as n-hezrane, n-pentane, naheptane, iso-heptane, n-decane, and the like, unsubstituted or alkyl substituted cycloalkyl hydrocarbons and aromatic hydrocarbons such a benzene, toluene, xylene, naphthalene, and the like. Any diluent of the above .type which is liquid under the reaction conditions can be employed. However, it must be remembered that when an aromatic diluent is used the telemeriza-tion reaction of the invention will take place with it, and accordingly, unless a mixture of polyalkylated compounds having different aromatic nuclei is specifically desired, the aromatic diluent should be the same as the aromatic hydrocarbon reactant, i.e; the aromatic hydrocarbon reactant can also be employed in larger quantities to serve as a diluent for the reaction. The quantity of diluent employed is not important although a diluent to total products ratio of from 0.4 to 9.5 (voL/wt.) is usually employed.

The above reaction temperature is not critical although temperatures above 120 F. should not be used since such temp eratures result in rapid deactivation of the telomerina-lion catalyst. The pressure is normally atmospheric, or eve-n subatmospheric although more elevated pressures can be used if desired, such as to keep a relatively low boiling diluent from vaporizing.

GENERAL PROCEDURE About 900 cc. of dry solvent was put in the reactor,

which was blanketed with dry nitrogen; the metal alkyl compound was dissolved in 100 cc. of solvent and the solution was introduced to the reactor through a pressure equalized funneL- The alkyl ha'locyclopentane was added prior to the addition of the metal halide compound, which was TiCl in all of the examples.

The above system was stirred, usually for about minutes, until it acquired a brownish color. At this stage, the aromatic telogen Was added and immediately after this, ethylene was introduced at a rate of 1.75 to 1.90 g. per minute. In some cases, a small amount of nitrogen 10 to 700 F. n.b.p., or distilled in a /5 column and high vacuum to separate light and heavy fractions.

1 n= C for n-Heptane; MOP for methylcyclopentane. 1 Approximate value.

8 Stripped to 700 F. I.B.P.

4 Less than .5% on total products.

5 Stripped to 700 F. vapour temperature.

0 At -10 F., using 2+1 vol. of methylisobutylketone.

Table I TELOMERIZATION REACTIONS OF ETHYLENE WITH LOWER AROMATICS I II III IV V VI VII VIII Reactants:

Ethylene, c 01 248 105 128 105 92 110 Aromatic telogenype NOl'le CcHo CuH5CHa CsHs-CHs CuHa-CHa CflHo CsHs 05H" Amount, I! 110 135 108 108 110 110 110 Catalyst:

Metal alkyl compound:

Type EtAlOlz EtaAlOl EtAlCli EtAlCli EtAlClz EtAlCli EtAlCl EtAlOl, Amount 28 14 28 28 28 28 Alkyl aluminum/TiCli, mol. ratio 1.22 .69 69 1. 61 .69 69 .69 Methyl chlorooyclopentane, g 0 0 Metal alkyl methylchlorocyclopentane, mol.

ratio 1. 74 1. 74 1. 74 1. 74 1. 74 1. 74 Solvent:

Type 1 11:01 MOP 1 MOP MOP MOP MOP MOP MOP Amount, cc 900 1000 1000 1000 1000 1000 900 1000 Conditions:

Reaction temp, F 54 77 75 52 48 124 Reaction time, min 138 50 60 73 60 50 60 Ethylene rate of charge, g./min 1 1.76 1.82 9 1. 75 1 1. 75 1 l. 75 2 1. 75 1. 83 1. 83 Total ethylene adsorption, g 91 75 60 92 Products:

Light materials, g 18 15 Oil, gfi 16 45 207 82 57 107 89 87 Solids, g 4 Trace 42 Trace Trace Trace Trace Trace Trace Inspections of the oil:

Vis. SUS at 210 F 49 44 50 49 39 V I 133 125 128 Pour point, F 5 +55 +5 Silica gel aromatics, weight percent- 36. 4 31. 7 17. 6 Bromine number Hivac bottoms, weight percent Dewaxing:

Wax, weight percent 90 3 Inspections of the oil:

Vis. SUS at 210 F 60 V I 117 Pour point, F 20 IX X XI XII XIII XIV XV XVI XVII React-ants:

Ethylene, g 92 95 90 90 92 95 536 93 92 Aromatic tel Type CaHa CaHa 01H C0110 C6 10 Cs t CoHa CrHo CsHs C 1 Amount, g 110 110 800 110 110 110 165 110 110 ate Metal alkyl compound pe EtAIOlz Et AlCl EtiAlCl EtiAl EtiAl EtaAl EtAlClz Et Al EtiAl Amount. 28 14 14 7. 7 7. 7 7. 7 7 7. 7 7. 7 Alkyl aluminum/T1014, 69 35 35 .206 .206 206 69 .303 1. 77 Methyl chlorocyclopentaue, g Metal alkyl methylchlorocyclo io 1. 74 91 91 52 52 52 1. 74 52 52 Solvent:

Type n=C1 MOP None n=O n=O MOP MOP n=O n=c Amount, cc 1000 1000 1000 1000 1000 1000 1000 1000 Conditions:

Reaction temp., F 71 71 70 124 60 71 70 70 70 Reaction time, 50 50 50 50 50 50 293 50 50 Ethylene rate of charge, g./min 1. 83 1.89 1. 81 1. 81 2 1.83 1.89 1.83 1. 85 1 1. 83 Total ethylene adsorption, g 92 95 90 90 92 05 93 Products:

Light materials, 2 Oi], g3 78 64 81 85 384 62 Solids, g Trace Trace Trace 12 4 Trace Trace 7 Trace Tr ce Inspections of the oil:

Vis. SUS at 210 F 65 5 66 5 66 40 62 53 52 VI 118 123 89 131 136 136 Pour point, F 20 +25 30 +70 +25 +35 Silica gel aromatics, weight percent Bromine numben Hivac bottoms, weight percent Dewaxing: 6

Wax, Weight percent 9 9. 8 11 3. 2 Inspections of the oil: Vis. SUS at 210 F 53 51 62 50 V1 132 133 129 121 Pour point, F 5 5 -5 Table II PROPERTIES OF DISTILLATION CUTS (Example III) Dewax- Aroing at Weight percent on Atm. vapor matics, V-2l0 v.1. F

total charge temp, F. weight wax,

percent weight percent 1. 250/467 5 d1stillation--.. 467/729 1 Silica gel (Humble short cut method). I Atter dewaxing at 10 F.

The above oils of Examples III-XVII of Table I were subjected to nuclear magnetic resonance and mass spectroscopic analyses, and the oils were found to be highly a-lkyl ated benzenes. The average molecule in them showed that the benzene nucleus was substituted at from 3.7 to 5.2 points, by straight chains of from 3.6 to 9.5 carbon atoms in average length. Examples I and II were included for comparison purposes. Example I shows the polymerization of ethylene in the absence of an aromatic telogen and methyl chlorocyclopentane. The product of this run was about wax. Example II shows the polymerization of ethylene in the presence of an aromatic telogen but in the absence or methyl chlorocyclopentane. The product of this run contained almost 50% s0lids which, f course, are of no use as lubricating oils and must be separated from the oil fraction.

It can also be seen from the above examples that the process of the invention provides a simple direct method for preparing high viscosity index lubricating oils from simple and inexpensive starting materials. Additionally, lube oils of any desired structure can be prepared by employing suitable multiple ring aromatic starting materials. A further important advantage of the products of the invention is their freedom from trace impurities such as sulfur and nitrogen compounds, normally encountered in petroleum rractions.

Modifications of the process of the invention can 'be made without departing from the scope and spirit of the instant invention.

What is claimed is:

1. The process of preparing a polyalkyl ated aromatic hydrocarbon comprising the steps of reacting an aromatic hydrocarbon with ethylene in the presence of a minor amount of a S-component catalyst comprising (1) an alkyl compound of a metal of groups I-III of the periodic table, (2) a halide of a metal of groups IV-B, V-B, VIB and VIII of the periodic table, and (3) an alkyl halocyclopentane 'Wherein the alkyl group contains from 1-10 carbon atoms, in an inert hydrocarbon diluent in the range of 0 to 130 F.; the quantity of alkyl halocyclopentane being less than one mole per mole of alkyl radical of catalyst component (1).

2. The process of claim 1 wherein catalyst component (1) is an alkyl aluminum compound.

3. The process of claim 2 wherein catalyst component (2) is a titanium halide.

4. The process of claim 3 wherein catalyst component (3) is methylchlorocyclopentane.

5. The process of preparing a polyalkylated aromatic hydrocarbon comprising the steps of reacting an aromatic hydrocarbon with ethylene in the presence of a 3-component catalyst comprising (1) titanium tetrachloride, (2) an alkyl aluminum compound and 3) methylchl-orocyclopentane in an inert hydrocarbon diluent at a temperature in the range of 0-130 F.; the quantity of halocyclopentane being less than one mole per mole of alkyl radical of catalyst component (2).

6. The process of claim 5 wherein the temperature is in the range of 30 to F.

7. The process of claim 5 wherein the hydrocarbon diluent is methylcyclopentane.

8. The process of claim 1 wherein the ratio of catalyst component (1) to catalyst component (2) is in the range of 0.1 to 5.0.

References Cited in the file of this patent UNITED STATES PATENTS 2,824,145 McCall et al Feb. 18, 1958 2,907,805 Bestain et a1. Oct. 6, 1959 2,935,542 Minckler et al May 3, 1960 2,969,408 Nowlin et a1 Ian. 24, 1961 2,993,942 White et a1. July 25, 1961 

1. THE PROCESS OF PREPARING A POLYALKYLATED AROMATIC HYDROCARBON COMPRISING THE STEPS OF REACHING AN AROMATIC HYDROCARBON WITH ETHYLENE IN THE PRESENCE OF A MINOR AMOUNT OF A 3-COMPONENT CATALYST COMPRISING (1) AN ALKYL COMPOUND OF A METAL OF GROUPS I-III OF THE PERIODIC TABLE, (2) A HALIDE OF A METAL OF GROUPS IV-B, V-B, VI-B AND VIII OF THE PERIODIC TABLE, AND (3) AN ALKYL HALOCYCLOPENTANE WHEREIN THE ALKYL GROUP CONTAINS FROM 1-10 CARBON ATOMS, IN AN INERT ALKYL GROUP CONTAINS FROM THE RANGE OF 0 TO 130* F., THE QUANTITY OF ALKYL HALOCYCLOPENTANE BEING LESS THAN ONE MOLE PER MOLE ALKYL RADICAL OF CATALYST COMPONENT (1). 